WO2024004613A1 - Iron–nickel alloy foil, method for manufacturing iron–nickel alloy foil, and component - Google Patents

Iron–nickel alloy foil, method for manufacturing iron–nickel alloy foil, and component Download PDF

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WO2024004613A1
WO2024004613A1 PCT/JP2023/021715 JP2023021715W WO2024004613A1 WO 2024004613 A1 WO2024004613 A1 WO 2024004613A1 JP 2023021715 W JP2023021715 W JP 2023021715W WO 2024004613 A1 WO2024004613 A1 WO 2024004613A1
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alloy
alloy foil
pal
deformation
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French (fr)
Japanese (ja)
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准平 大山
光治 米村
元 中村
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日鉄ケミカル＆マテリアル株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon

Definitions

  • the present invention relates to Fe--Ni metal foil, a method for producing Fe--Ni metal foil, and parts using the Fe--Ni alloy foil.
  • Fe-Ni alloy foil which has good etching and thermal expansion properties, is used for metal masks that are essential for manufacturing organic light-emitting diodes (OLEDs), but as pixel density increases, thinner metal masks are required.
  • Patent Document 2 In response to the demand for thinner Fe-Ni alloy foils, Fe-Ni alloy foils with a thickness of 100 ⁇ m or less are on the market, and there is a demand for Fe-Ni alloy foils with a thickness of even less than 50 ⁇ m. .
  • the present invention aims to suppress deformations such as ear waves, mid-elongation, and warping in Fe-Ni alloy foil with a thickness of 50 ⁇ m or less. , sometimes simply called alloy foil).
  • Alloy plate made by rolling (Although there is no clear standard for the thickness of alloy foil and alloy plate, for example, a plate with a thickness of more than 100 ⁇ m may be called an alloy plate, and a plate with a thickness of 100 ⁇ m or less may be called an alloy foil.Hereinafter, a plate made thinner by rolling A plate-shaped Fe-Ni alloy with a thickness of 100 ⁇ m or more before being made into an alloy foil is sometimes referred to as a Fe-Ni alloy plate or simply an alloy plate.) The dislocations and vacancies in it move and deform. Dislocations themselves are generated by the movement and combination of vacancies. Based on these facts, the inventors focused their attention on the behavior of pores in the alloy plate. Note that the vacancies in the present invention do not mean defects such as shrinkage pores or gas vacancies during solidification in a cast product, but atomic vacancies or point defects.
  • PAL positron annihilation lifetime
  • the present invention has been made based on the above findings, and its gist is as follows.
  • the ingredients are mass%, C: 0 to 0.030%, Si: 0 to 0.21%, Mn: 0 to 0.30%, Ni: 30.0 to 60.0%, Co: 0-5.00%, P: 0.01% or less, S: 0.01% or less, and the remainder is Fe and impurities,
  • An Fe--Ni alloy foil having a thickness of 50 ⁇ m or less and a positron annihilation life (PAL) of 0.150 ns or more.
  • PAL positron annihilation lifetime
  • [3] The Fe-Ni alloy foil according to [1] or [2], having a plate thickness of 20 ⁇ m or less.
  • [4] The method for producing Fe-Ni alloy foil according to any one of [1] to [3] above, The ingredients are mass%, C: 0 to 0.030%, Si: 0 to 0.21%, Mn: 0 to 0.30%, Ni: 30.0 to 60.0%, Co: 0-5.00%, P: 0.01% or less, A step of preparing Fe-Ni alloy powder in which S: 0.01% or less and the balance is Fe and impurities; A Fe-Ni alloy ingot manufacturing step of manufacturing an Fe-Ni alloy ingot by the HIP method from the Fe-Ni alloy powder; A method for producing Fe--Ni alloy foil, comprising a rolling step of rolling the Fe--Ni alloy ingot.
  • an Fe--Ni alloy foil that suppresses deformations such as ear waves, mid-elongation, and warping.
  • FIG. 3 is a diagram showing an example of the relationship between PAL and deformation amount in Fe--Ni alloy foil.
  • FIG. 3 is a diagram showing an outline of a vertical hanging test.
  • FIG. 2 is a conceptual diagram for explaining an example of a method for measuring a gap created between a test piece and a vertical plane in a vertical hanging test.
  • Positron annihilation lifetime is an index used to evaluate lattice defects including vacancies in materials such as metal materials and polymer materials. It is also sometimes referred to as the average positron annihilation lifetime.
  • PAL can evaluate the type of lattice defects.
  • PAL is a comprehensive index of the number of pores and the size of pores in a material. In the present invention, vacancies refer to atomic vacancies and point defects, rather than defects such as shrinkage pores or gas vacancies during solidification in cast products. A detailed explanation of the PAL will be omitted here, but the larger the pore size, the longer the PAL.
  • the detected relative intensity (the number of counts of ⁇ rays emitted when a positron annihilates, which corresponds to the probability of existence) increases; As a result, the pore size also increases and the PAL becomes longer.
  • Positron annihilation lifetime can be measured with a PAL measuring device.
  • PAL measuring device a commercially available device such as a positron annihilation life measuring device manufactured by Techno-AP can be used.
  • the inventors performed evaluation using a positron annihilation life measuring device manufactured by Techno-AP Co., Ltd. using 22 Na as a positron beam source.
  • Fe-Ni alloy foil which is the material to be evaluated, was cut into 10 mm squares, two sets of three stacked sheets were prepared, and the positron beam source was sandwiched between the three stacked Fe-Ni alloy foils. This was wrapped and fixed in aluminum foil to create a sample for PAL measurement.
  • the prepared measurement sample is applied to a measuring device to measure the positron annihilation lifetime (PAL). It is also advisable to use the data analysis software that comes with the measuring device (for example, PALSfit3 developed by the Technical University of Denmark). In the measurement, in order to take into account the effects of the lifespan of the Kapton film (0.3800 ps), the lifespan of the epoxy resin (1.9044ps), etc., it is preferable to fix these lives for analysis.
  • PAL positron annihilation lifetime
  • hot powder metallurgy methods such as the HIP method can eliminate shrinkage pores and gas vacancies, but cannot eliminate atomic vacancies.
  • Materials manufactured by hot powder metallurgy are isotropically compressed and sintered at high temperatures, so it is thought that a large number of pores are uniformly generated within the material. .
  • the pores diffuse, causing neck portions between particles to grow and sintering to proceed.
  • materials manufactured by hot powder metallurgy have a microstructure in which pores are present, unlike materials manufactured by conventional melting methods.
  • the vacancies are used for the upward movement of edge dislocations, and the arrangement of the vacancies plays a role in forming dislocations. Therefore, in the structure of a hot powder metallurgy material with a long positron annihilation life and a large proportion (large amount) of vacancies, vacancies move easily and form dislocations, and dislocations can move while absorbing many vacancies. Therefore, it is thought that the structure has a relatively easy movement of dislocations. The ease with which such dislocations form and move affects the stress relaxation of the material. In addition, the remaining vacancies that are not used for dislocations act similarly to solid solution strengthening and contribute to the basic strength.
  • melt-molded materials have a short positron annihilation life and a small proportion (amount) of vacancies, so edge dislocations are difficult to move upward, and dislocations are difficult to move. In other words, dislocations are distributed non-uniformly in melt-sawn material and it is difficult to move, so residual stress is non-uniform and shape defects are likely to occur.
  • the PAL of conventional melt-molded materials does not exceed 0.150 ns, but the PAL of hot powder metallurgy materials exceeds 0.150 ns. That is, in the case of a material whose defects are mainly dislocations, such as conventional melt-molded materials, the PAL is less than 0.150 ns, and in the case of materials whose defects are mainly point defects such as pores, such as hot powder metallurgy materials, the PAL is less than 0.150 ns. It was confirmed that the time was 0.150 ns or more. Therefore, it is considered that the PAL of 0.150 ns or more indicates that the lattice defects are mainly point defects such as vacancies. That is, it is considered that PAL 0.150 ns is the boundary at which the microstructure changes from a dislocation-based microstructure to a vacancy-based microstructure.
  • the present inventors adopted the following test method to evaluate the amount of deformation by a vertical hanging test. That is, a test piece is prepared by cutting an alloy foil into strips with a width of 40 mm and a length of 250 mm, and this is hung on a vertical surface plate (a surface plate having a plane parallel to the vertical direction (vertical plane)). It is preferable to actually measure the amount of gap between the plane and the test piece, and evaluate the amount of deformation using the maximum value. Since ear waves and mid-elongation usually occur along the rolling direction, it is preferable to set the long side of the test piece in the rolling direction.
  • alloy foil when manufacturing alloy foil, it may be wound into a coil shape, and in order to eliminate the winding tendency that occurs at that time, it is recommended to apply a certain tension. For example, if the test piece is 50 ⁇ m or less thick and 40 mm wide, a 100 g weight may be attached to the lower end of the test piece to generate tension.
  • the method for measuring the gap between the test piece and the vertical plane is not particularly limited, but it can be measured using a gap gauge, laser length measurement, image analysis using photography, or the like.
  • FIG. 1 shows an example of the relationship between PAL and deformation amount using Fe--Ni alloy foil shown in Examples.
  • FIG. 1 shows the relationship between PAL and deformation amount using a 30 ⁇ m thick Fe-Ni alloy foil.
  • FIG. 1 it was confirmed that there is a strong correlation between the amount of deformation and PAL, and that the amount of deformation decreases as PAL becomes longer. That is, it was confirmed that the deformation of the alloy foil could be suppressed by changing the type of lattice defects from a structure mainly composed of dislocations (PAL of less than 0.150 ns) to a structure mainly composed of vacancies (PAL of 0.150 ns or more).
  • the lower limit of PAL is preferably 0.151ns, 0.152ns, 0.153ns, 0.154ns, 0.155ns, 0.156ns, 0.157ns, 0.158ns, 0.159ns, 0.160ns, 0
  • the length may be .161ns, 0.162ns, 0.163ns, 0.164ns, or 0.165ns.
  • the longer the PAL the smaller the amount of deformation.
  • the PAL becomes long to a certain extent, large pores will be present, and there is a possibility that the large pores will become the starting point of destruction. From experiments conducted by the present inventors, there were no actual PAL values exceeding 0.200 ns for practical hot powder metallurgy materials. Therefore, although there is no need to specifically limit the upper limit value of PAL, when setting the upper limit value, it is 0.200 ns, preferably 0.198 ns, 0.196 ns, 0.194 ns, 0.192 ns, 0.190 ns, 0. It is preferable to set it to 188ns, 0.186ns, 0.184ns, 0.182ns, or 0.180ns.
  • C 0 to 0.030%
  • Carbon (C) increases the strength of the alloy foil.
  • the C content is preferably 0.030% or less. Preferably, it is 0.028%, 0.026%, 0.024%, 0.022%, or 0.020%.
  • Si 0-0.21% Silicon (Si) increases the coefficient of thermal expansion of the alloy.
  • Fe--Ni alloy foil is an alloy that is originally expected to have a low coefficient of thermal expansion, and may be used in a temperature environment of about 200° C., depending on its use. Furthermore, if the Si content is too high, the strength will become too high and the workability of the alloy will decrease. Therefore, from the viewpoint of suppressing thermal expansion and workability, the Si content is preferably 0.21% or less. Preferably, it is 0.20% or less, 0.18% or less, 0.16%, 0.14%, 0.12%, or 0.10% or less.
  • Mn 0 to 0.30%
  • Manganese (Mn) is used as a deoxidizer instead of Mg and Al to avoid spinel formation.
  • Mn content is preferably 0.30% or less.
  • the preferred range of Mn content is 0.28% or less, 0.26% or less, 0.24% or less, 0.22% or less, 0.20% or less, 0.18% or less, or 0.16% or less. It's good to do that.
  • Nickel (Ni) is a main component that keeps the coefficient of thermal expansion of the alloy low, and if the Ni content is too low, the body-centered cubic (BCC) structure will increase and the behavior of dislocations will change.
  • BCC body-centered cubic
  • the Ni content is preferably 60.0% or less.
  • the preferable range of Ni content is 31.0% or more, 31.5% or more, 32.0% or more, 32.5% or more, 33.0% or more, 33.5% or more, 34.0 on the lower limit side.
  • Co 0-5.00%
  • Co is a component that can further reduce the coefficient of thermal expansion of the alloy as its addition amount increases in relation to the amount of Ni.
  • impurities In addition to the above elements, the remainder is Fe (iron) and impurities. Impurities are elements that are unintentionally included during the manufacturing process. In particular, impurities include components such as P and S. It is preferable that the content of P and S is limited within the following range.
  • P 0.010% or less
  • P segregates at grain boundaries during solidification and increases susceptibility to solidification cracking. Therefore, it is preferable that the P content be as low as possible. Therefore, the P content is limited to 0.010% or less.
  • the content is preferably 0.005% or less, or 0.003% or less.
  • the lower limit of the P content is 0%, in reality it may be 0.001% or more, since reducing it excessively increases manufacturing costs.
  • S 0.010% or less
  • S segregates at grain boundaries during solidification and increases susceptibility to solidification cracking. Therefore, it is preferable that the S content be as low as possible. Therefore, the S content is limited to 0.010% or less. Preferably, it is 0.005% or less, or 0.002% or less. Although the lower limit of the S content is 0%, in reality it may be 0.001% or more, since reducing it excessively increases manufacturing costs.
  • Other elements may also be contained as impurities as long as they do not impair the effects of the present invention.
  • Examples include Cr, Al, Cu, Nb, Mo, Ti, Mg, Ca, Sn, V, W, Zr, B, Bi, and the like.
  • the thickness of the Fe--Ni alloy foil is not particularly limited. Although an alloy plate with a thickness of 100 ⁇ m or less is called an alloy foil, it may also be applied to an alloy plate with a thickness of 100 ⁇ m or more. However, in general, the thinner the plate, the more likely deformations such as ear waves, elongation, and warping occur. Therefore, it is more effective to apply the present invention to Fe--Ni alloy foil with a thickness of 50 ⁇ m or less.
  • the lower limit of the plate thickness is not particularly limited, the plate thickness may be 1.0 ⁇ m or more from the viewpoint of industrial manufacturability.
  • the method for manufacturing the Fe--Ni alloy foil according to the present invention is not particularly limited. However, the life of PAL can be extended by making improvements mainly in the manufacturing process, rolling process, and annealing process of the alloy ingot. The method will be explained below. Note that the Fe--Ni alloy foil according to the present invention is not limited to the manufacturing method described herein.
  • the manufacturing process of an Fe-Ni alloy ingot is a process of obtaining a Fe-Ni alloy ingot (steel billet, slab, etc.) having a predetermined composition.
  • a Fe-Ni alloy ingot steel billet, slab, etc.
  • melting method a method of refining and solidifying a molten Fe--Ni alloy
  • metal powders having a predetermined composition are combined and solid phase bonded under high temperature and high pressure such as HIP (Hot Isostatic Press), a so-called hot powder metallurgy method.
  • the alloy ingot of ingot material (ingot alloy ingot) produced by the conventional ingot manufacturing method has almost no pores, and the main lattice defects are dislocations. Furthermore, in the case of melt-sawn materials, dislocations are not uniformly introduced throughout the material during the solidification process. To put it simply, the way in which dislocations are introduced is different between the surface and the center of a melted alloy ingot.
  • the main defect is dislocation
  • the stress concentration due to processing exceeds the yield stress
  • dislocation occurs and the stress is relaxed by plastic deformation. Therefore, when dislocations are non-uniformly introduced into the material of a melt-produced alloy, stress relaxation occurs locally, and residual stress tends to occur non-uniformly.
  • hot powder metallurgy methods such as the HIP method
  • shrinkage pores and gas vacancies can be eliminated, but atomic vacancies cannot be eliminated.
  • Materials manufactured by hot powder metallurgy are isotropically compressed and sintered at high temperatures, so it is thought that a large number of pores are uniformly generated within the material. .
  • the pores diffuse, causing neck portions between particles to grow and sintering to proceed.
  • a material manufactured by hot powder metallurgy has a microstructure in which pores are present, unlike ingot material. Therefore, a hot powder metallurgy method such as the HIP method can produce an alloy ingot with a uniformly larger number of pores and a longer PAL life than the conventional melting method.
  • the manufacturing method is not particularly limited.
  • a conventionally used HIP method can be applied.
  • the metal powder used as the raw material for the HIP method is finely grained.
  • the particle size of the metal powder is preferably 500 ⁇ m or less, 400 ⁇ m or less, 300 ⁇ m or less, 200 ⁇ m or less, or 100 ⁇ m or less.
  • the method for producing metal powder is also not particularly limited. An alloy powder can be obtained by applying an atomization method or the like to a molten metal that has been adjusted to a predetermined composition using a conventional refining method.
  • the refining method at this time is also not particularly limited. At the laboratory level, it can also be carried out in a vacuum induction furnace. In order to reduce the amount of carbon, gas components, and metal inclusions, AOD (Argon-Oxygen-Decarburization) method, VOD (Vacuum-Oxygen-Decarburization) method, V-AOD method, etc. can be applied.
  • a desired alloy ingot can be obtained by placing the prepared alloy powder in a metal container and subjecting it to HIP treatment.
  • hot powder metallurgy such as HIP
  • An alloy foil can be obtained by hot rolling or cold rolling the obtained Fe--Ni alloy ingot.
  • an Fe--Ni alloy ingot can be hot-rolled into a Fe--Ni alloy plate with a thickness of 1 mm or less, and then cold-rolled to obtain an alloy foil with a desired thickness.
  • Conventional manufacturing methods can be used for both hot rolling and cold rolling.
  • the total reduction ratio of each pass of cold rolling is not too large. This is because if the total reduction ratio of cold rolling is too large, a rolled structure with a high dislocation density in which strain is accumulated due to rolling is formed, and pores are likely to be consumed. It is preferable to design a process that allows for mild rolling with a lower total cold rolling reduction within a range that does not reduce the work hardening ability.
  • dislocations are reintroduced by subsequent rolling, but the dislocation density is not as high as in the unannealed rolled structure, so the dislocations are easy to move, and the dislocations cut together, creating vacancies and increasing the dislocation density. also increases. As a result, the life of PAL is extended. Therefore, it is preferable to perform annealing, and it is particularly preferable to perform intermediate annealing between rolling.
  • annealing it is preferable to eliminate dislocations by annealing, but dislocations will not disappear if recrystallization is not involved. Therefore, it is desirable to perform annealing at a temperature higher than the recrystallization temperature as much as possible.
  • a temperature higher than the recrystallization temperature for example, in the case of Fe-Ni alloy or stainless steel, it is preferable to anneal at a temperature of 700° C. or higher.
  • the temperature is 750°C or higher, or 800°C or higher.
  • the Fe--Ni alloy foil according to the present invention can be used as a material for all kinds of parts, since deformation is suppressed even when the foil is thinned.
  • electronic devices such as battery materials
  • thin alloy foils due to the need for lighter weight, higher functionality, and higher strength, and it is preferable to apply them to these component materials.
  • the Fe--Ni alloy foil according to the present invention may be applied to a metal mask of an OLED. Fe-Ni alloy foil is used for OLED metal masks due to its etchability and low thermal expansion properties to achieve higher definition. be.
  • parts used to manufacture electronic parts, such as metal masks, rather than electronic parts or mechanical parts themselves, are also included in parts.
  • the parts having Fe-Ni alloy foil according to the present invention include not only parts manufactured from Fe-Ni alloy foil but also parts having parts made of Fe-Ni alloy foil.
  • Test material A Fe-Ni alloy ingot based on Fe-36Ni alloy and adjusted to the composition shown in Table 1 was prepared as a HIP material by the HIP method and as a melt-molten material in accordance with a conventional manufacturing method. Note that the remainder of the components in Table 1 are Fe and impurities.
  • HIP material molten metal (molten alloy) adjusted to the composition shown in Table 1 was made into spherical alloy powder by gas atomization. The obtained alloy powder was classified, and the 300 ⁇ m unsieved product was subjected to HIP treatment to obtain a HIP material. The HIP treatment was carried out according to the usual procedure, and the HIP material was manufactured by holding the HIP treatment at a high temperature and pressure of 1150° C. and 120 MPa for 3 hours. As shown in Table 1, HIP1 and HIP2 were prepared as HIP materials with different components.
  • a comparative material continuously cast slab material conforming to the conventional manufacturing method is made by solidifying molten metal adjusted to the composition shown in Table 1, and then further using the ESR method (electro slag remelting method) or the VAR method (vacuum arc remelting method). After refining using the melting method), a slab was obtained according to the conventional continuous casting method. As shown in Table 1, ingot material 1 and ingot material 2 were prepared as ingot materials having different components.
  • test material was subjected to processing such as rolling and annealing to form an alloy foil.
  • Table 2 shows the processing conditions for each test material.
  • the HIP1 and HIP2 test materials were machined into rectangular parallelepiped shapes with thicknesses of 1 mm, 3 mm, 10 mm, and 50 mm to obtain alloy plates.
  • the 50 mm thick alloy plate was hot rolled into a 3 mm thick alloy plate. Alloy plates of other thicknesses were not hot rolled.
  • the thus obtained alloy plates with thicknesses of 1 mm, 3 mm, and 10 mm were cold rolled to obtain Fe--Ni alloy foils with a final plate thickness of 30 ⁇ m (0.030 mm).
  • two types were prepared: one in which intermediate annealing was performed during cold rolling, and the other in which intermediate annealing was not performed.
  • the slab thickness after continuous casting is 250 mm, and then hot rolling is performed to form an alloy plate with a thickness of 300 ⁇ m (0.300 mm), (intermediate) cold rolling, intermediate An Fe-Ni alloy foil with a final thickness of 30 ⁇ m (0.030 mm) was obtained by annealing and (final) cold rolling.
  • Test piece 1 was prepared by cutting alloy foil into strips with a width of 40 mm and a length of 250 mm (cut so that the longitudinal direction was in the rolling direction), and this was placed on a vertical surface plate (a plane parallel to the vertical direction (vertical plane)). It was suspended on a vertical plane 3 of a surface plate 2 having a surface plate. The amount of the gap 5 between the vertical plane 3 and the test piece 1 was actually measured, and the maximum value was evaluated as the amount of deformation.
  • a 100 g weight was attached to the lower end of the test piece to generate tension 4, and a gap 5 was created between the test piece 1 and the vertical plane 3 of the vertical surface plate 2 as shown in FIG. (within the dotted line frame) was measured using a gap gauge (not shown).
  • the range 6 in which the gap 5 is measured is not particularly limited, it is preferable to set the entire width of the vertical plane 3 as the measurement range 6, which is also the case in this embodiment.
  • Each gap was measured four times and the average was taken as the amount of deformation of the gap, and the maximum value of the amount of deformation of each gap was evaluated as the amount of deformation of the test piece.
  • the average positron annihilation life is calculated by cutting the Fe-Ni alloy foil of each test material into 10 mm squares, preparing two sets of three stacked sheets, and placing three sheets of positron beam source.
  • a sample for PAL measurement was prepared by sandwiching between two layers of Fe--Ni alloy foil, and wrapping and fixing this with aluminum foil.
  • the prepared measurement sample was applied to a measuring device to measure the positron annihilation lifetime (PAL).
  • the evaluation was carried out using a positron annihilation lifetime device manufactured by Techno AP as a PAL measuring device and using 22 Na as a positron beam source.
  • the data analysis software used was PALSfit3 developed by the Technical University of Denmark. In order to take into account the effects of Kapton membrane life (0.3800 ps) and epoxy life (1.9044 ps) during the measurement, these lives were fixed and the average positron annihilation life of the material was analyzed for one component.
  • Table 2 shows the manufacturing conditions, amount of deformation, and measurement results of PAL (average positron annihilation life) of each test material.
  • the relationship between the amount of deformation shown in Table 2 and PAL is illustrated in FIG.
  • the triangular mark in FIG. 1 indicates a comparative example (molten material), and the circular mark indicates an example (HIP material).
  • the present invention can be utilized for Fe-Ni alloy foil.
  • the effect is particularly noticeable when used for ultra-thin Fe--Ni alloy foils with a thickness of 50 ⁇ m or less.
  • Test piece 2 Vertical surface plate 3 Vertical plane 4 Tension (direction) 5 Gap 6 Measuring range

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Abstract

The present invention addresses the problem of suppressing deformation such as edge waves, center waves, and warping from occurring in an ultra-thin (50 μm or less in thickness) iron–nickel alloy foil, and the purpose of the present invention is to obtain an iron–nickel alloy foil in which such deformation is suppressed. This iron–nickel alloy foil has a positron annihilation lifetime (PAL) of at least 0.150 ns and can reduce the amount of deformation (the total evaluated amount of deformation such as edge waves, center waves, and warping) relative to conventional products. In order to form a primarily vacant microstructure to achieve a PAL of at least 0.150 ns, an iron–nickel alloy foil can be obtained by manufacturing an alloy block (slab) by HIP treatment and rolling and heat treating the alloy block in accordance with conventional methods.

Description

Ｆｅ－Ｎｉ合金箔、Ｆｅ－Ｎｉ合金箔の製造方法、および部品Fe-Ni alloy foil, Fe-Ni alloy foil manufacturing method, and parts
　本発明はＦｅ－Ｎｉ金属箔とＦｅ－Ｎｉ金属箔の製造方法、およびそのＦｅ－Ｎｉ合金箔を用いた部品に関する。 The present invention relates to Fe--Ni metal foil, a method for producing Fe--Ni metal foil, and parts using the Fe--Ni alloy foil.
　電子機器の小型化および高密度実装化に伴い、電子機器を構成する各電子部品のダウンサイジング化や軽量化が要求される。例えば、二次電池用ケースとしてはアルミニウム箔（アルミ箔）やＦｅ－Ｎｉ合金箔を含むステンレス鋼箔（ステンレス箔）が適用されている。二次電池の軽量、薄型化のためケース板厚の薄化も追及されているが、強度も維持確保することが要求されている。そのため、従来のアルミ箔からステンレス箔にして強度を維持しつつ薄厚化が進められている（例えば特許文献１）。 With the miniaturization and high-density packaging of electronic devices, there is a demand for downsizing and weight reduction of each electronic component that makes up the electronic devices. For example, aluminum foil (aluminum foil) and stainless steel foil (stainless steel foil) including Fe--Ni alloy foil are used as cases for secondary batteries. Although efforts are being made to reduce the thickness of the case plate in order to make secondary batteries lighter and thinner, it is also required to maintain and ensure strength. Therefore, progress is being made in replacing conventional aluminum foil with stainless steel foil to make it thinner while maintaining strength (for example, Patent Document 1).
　また、電子機器そのものに使用される部品ではなく、電子機器の製造に欠かせない素材や部品にも薄厚化が要求されている。例えば、有機発光ダイオード（ＯＬＥＤ）製造に欠かせないメタルマスクは、エッチング性や熱膨張性などの良好なＦｅ－Ｎｉ合金箔が適用されているが、高画素密度化に伴い、薄厚化が求められている（例えば特許文献２）。
　このようにＦｅ－Ｎｉ合金箔の薄厚化の要求に応え、板厚１００μｍ以下のＦｅ－Ｎｉ合金箔が流通しており、さらには板厚５０μｍをも下回るＦｅ－Ｎｉ合金箔が求められている。 Furthermore, thinning is required not only for parts used in electronic devices themselves, but also for materials and parts essential for manufacturing electronic devices. For example, Fe-Ni alloy foil, which has good etching and thermal expansion properties, is used for metal masks that are essential for manufacturing organic light-emitting diodes (OLEDs), but as pixel density increases, thinner metal masks are required. (for example, Patent Document 2).
In response to the demand for thinner Fe-Ni alloy foils, Fe-Ni alloy foils with a thickness of 100 μm or less are on the market, and there is a demand for Fe-Ni alloy foils with a thickness of even less than 50 μm. .
国際公開第２０１５／１２２５２３号International Publication No. 2015/122523 国際公開第２０２０／０６７５３７号International Publication No. 2020/067537
　Ｆｅ－Ｎｉ合金箔を薄厚化する場合、その製造過程（特に圧延）において不均一な残留応力が生じ易い。残留応力を除去するため圧延後に歪取り焼鈍などを行うが、最終的に残留応力を除去できず、耳波、中伸び、反りなどの変形の原因となう。この変形が、Ｆｅ－Ｎｉ合金箔の品質上の問題となっている。特に、板厚が５０μｍを下回るとこれら変形が顕在化し、品質上および技術上の重要な問題となっている。 When thinning Fe-Ni alloy foil, uneven residual stress is likely to occur during the manufacturing process (particularly rolling). In order to remove residual stress, strain relief annealing is performed after rolling, but ultimately the residual stress cannot be removed, causing deformations such as ear waves, mid-elongation, and warping. This deformation poses a quality problem for Fe--Ni alloy foil. In particular, when the plate thickness is less than 50 μm, these deformations become obvious and become an important problem in terms of quality and technology.
　そこで本発明は、厚さ５０μｍ以下のＦｅ－Ｎｉ合金箔において、耳波、中伸び、反りなどの変形を抑制することを課題とし、そのような変形の抑制されたＦｅ－Ｎｉ合金箔（以下、単に合金箔と呼ぶ場合がある。）を得ることを目的とする。 Therefore, the present invention aims to suppress deformations such as ear waves, mid-elongation, and warping in Fe-Ni alloy foil with a thickness of 50 μm or less. , sometimes simply called alloy foil).
　本発明者らは、上記課題を達成するため鋭意研究開発を続け以下の知見を得た。
（ア）耳波、中伸び、反りのような変形は合金箔中の変形の不均一性が要因であり、その変形の不均一性は合金箔内の残留応力の不均一性が原因であると考えた。残留応力は、合金箔の製造過程、特に圧延によって付与されることが知られている。圧延により合金板（合金箔と合金板の厚さには明確な基準はないが、例えば板厚１００μｍ超を合金板、板厚１００μｍ以下を合金箔と呼んでもよい。以下、圧延により薄厚化した合金箔になる前の厚さ１００μｍ以上の板状のＦｅ－Ｎｉ合金をＦｅ－Ｎｉ合金板、または単に合金板と呼ぶ場合がある。）中の転位や空孔が移動して変形する。転位自体は空孔の移動・結合により生成するものである。これらのことから、発明者らは合金板中の空孔の挙動に着目した。なお、本発明での空孔は、鋳造品における凝固時の収縮孔やガス空孔の類の欠陥ではなく、原子空孔や点欠陥を意味する。 In order to achieve the above-mentioned object, the present inventors have continued to conduct research and development and have obtained the following knowledge.
(a) Deformations such as ear waves, elongation, and warping are caused by non-uniform deformation within the alloy foil, and non-uniformity of deformation is caused by non-uniformity of residual stress within the alloy foil. I thought. It is known that residual stress is imparted during the manufacturing process of alloy foil, particularly during rolling. Alloy plate made by rolling (Although there is no clear standard for the thickness of alloy foil and alloy plate, for example, a plate with a thickness of more than 100 μm may be called an alloy plate, and a plate with a thickness of 100 μm or less may be called an alloy foil.Hereinafter, a plate made thinner by rolling A plate-shaped Fe-Ni alloy with a thickness of 100 μm or more before being made into an alloy foil is sometimes referred to as a Fe-Ni alloy plate or simply an alloy plate.) The dislocations and vacancies in it move and deform. Dislocations themselves are generated by the movement and combination of vacancies. Based on these facts, the inventors focused their attention on the behavior of pores in the alloy plate. Note that the vacancies in the present invention do not mean defects such as shrinkage pores or gas vacancies during solidification in a cast product, but atomic vacancies or point defects.
（イ）合金板中における空孔を均一に分散させれば、合金板の圧延に際し空孔の移動・結合が均一になり、変形挙動が合金板内で均一になると発想した。そこで、例えば熱間粉末冶金法（ＨＩＰ法など）により合金塊を製造し、これを圧延して合金箔を得て、変形挙動を評価した。その結果、耳波や中伸び、反りが抑制されていることを確認した。これにより、空孔を均一分散させた合金塊から圧延することにより、変形が抑制された合金箔が得られることを確認した。 (a) The idea was that if the pores in the alloy sheet were uniformly distributed, the movement and combination of the pores would be uniform during rolling of the alloy sheet, and the deformation behavior would be uniform within the alloy sheet. Therefore, an alloy ingot was manufactured by, for example, a hot powder metallurgy method (HIP method, etc.), and this was rolled to obtain an alloy foil, and the deformation behavior was evaluated. As a result, it was confirmed that ear waves, middle elongation, and warping were suppressed. As a result, it was confirmed that an alloy foil with suppressed deformation could be obtained by rolling an alloy ingot with pores uniformly dispersed therein.
（ウ）圧延板中の空孔の均一分散性の指標として、空孔の陽電子消滅寿命（ＰＡＬ：Ｐｏｓｉｔｒｏｎ　Ａｎｎｉｈｉｌａｔｉｏｎ　Ｌｉｆｅｔｉｍｅ）を用いることを考えた。ＰＡＬは、空孔数や空孔の大きさなどの総合的指標であり、空孔サイズが大きくなるほどＰＡＬが長くなり、空孔の数が多くなるほど検出される強度が大きくなる。空孔数が多くなると空孔同士の結合が生じ、結果として空孔サイズが大きくなる。発明者らは、実験によりＰＡＬが大きくなるほど、変形量が抑制されることを見出した。 (c) We considered using the positron annihilation lifetime (PAL) of pores as an index of the uniform dispersion of pores in a rolled sheet. PAL is a comprehensive index of the number of pores and the size of pores, and the larger the pore size, the longer the PAL, and the greater the number of pores, the greater the detected intensity. When the number of pores increases, the pores are bonded to each other, and as a result, the pore size increases. The inventors have found through experiments that the larger the PAL, the more the amount of deformation is suppressed.
（エ）Ｆｅ－Ｎｉ合金箔における実験により、ＰＡＬが０．１５０ｎｓ（ｎａｎｏ秒）以上であれば、従来の合金箔に比べ変形量が抑制されることを確認した。また、従来の合金箔はＰＡＬが０．１５０ｎｓ未満のものが多いことも確認した。これは、従来の合金塊の製造が溶製法であることに起因しているためと考えられる。溶製法の場合、凝固過程において空孔が凝集して刃状転位が生成しやすく、凝固後の合金塊中での空孔の均一性が阻害されるためと考えられる。 (D) Through experiments using Fe-Ni alloy foils, it was confirmed that when the PAL is 0.150 ns (nano seconds) or more, the amount of deformation is suppressed compared to conventional alloy foils. It was also confirmed that many conventional alloy foils have a PAL of less than 0.150 ns. This is thought to be due to the fact that conventional alloy ingots are manufactured using a melting method. This is thought to be because, in the case of the melt manufacturing method, pores tend to aggregate during the solidification process and edge dislocations are likely to be generated, which impedes the uniformity of the pores in the alloy ingot after solidification.
　本発明は上記知見に基づきなされたものであり、その要旨とするところは以下のとおりである。 The present invention has been made based on the above findings, and its gist is as follows.
［１］
　成分が、質量％で、
Ｃ　：０～０．０３０％、
Ｓｉ：０～０．２１％、
Ｍｎ：０～０．３０％、
Ｎｉ：３０．０～６０．０％、
Ｃｏ：０～５．００％、
Ｐ　：０．０１％以下、
Ｓ　：０．０１％以下、および
残部がＦｅおよび不純物であり、
板厚が５０μｍ以下であって、陽電子消滅寿命（ＰＡＬ）が０．１５０ｎｓ以上であることを特徴とするＦｅ－Ｎｉ合金箔。
［２］
　前記陽電子消滅寿命（ＰＡＬ）が０．１５０ｎｓ～０．２００ｎｓである［１］記載のＦｅ－Ｎｉ合金箔。
［３］
　板厚が２０μｍ以下の［１］または［２］に記載のＦｅ－Ｎｉ合金箔。
［４］
　前記［１］～［３］のいずれか１項に記載のＦｅ－Ｎｉ合金箔の製造方法であって、
成分が、質量％で、
Ｃ　：０～０．０３０％、
Ｓｉ：０～０．２１％、
Ｍｎ：０～０．３０％、
Ｎｉ：３０．０～６０．０％、
Ｃｏ：０～５．００％、
Ｐ　：０．０１％以下、
Ｓ　：０．０１％以下、および
残部がＦｅおよび不純物であるＦｅ－Ｎｉ合金粉末を準備する工程と、
前記Ｆｅ－Ｎｉ合金粉末をＨＩＰ法によりＦｅ－Ｎｉ合金塊を製造するＦｅ－Ｎｉ合金塊製造工程と、
前記Ｆｅ－Ｎｉ合金塊を圧延する圧延工程を含むことを特徴とするＦｅ－Ｎｉ合金箔の製造方法。
［５］
　さらに、前記圧延工程の各圧延パス間または最終圧延後に少なくとも１回の焼鈍工程を含む［４］に記載のＦｅ－Ｎｉ合金箔の製造方法。
［６］
　前記［１］～［３］のいずれか１項に記載のＦｅ－Ｎｉ合金箔を有する部品。 [1]
The ingredients are mass%,
C: 0 to 0.030%,
Si: 0 to 0.21%,
Mn: 0 to 0.30%,
Ni: 30.0 to 60.0%,
Co: 0-5.00%,
P: 0.01% or less,
S: 0.01% or less, and the remainder is Fe and impurities,
An Fe--Ni alloy foil having a thickness of 50 μm or less and a positron annihilation life (PAL) of 0.150 ns or more.
[2]
The Fe--Ni alloy foil according to [1], wherein the positron annihilation lifetime (PAL) is 0.150 ns to 0.200 ns.
[3]
The Fe-Ni alloy foil according to [1] or [2], having a plate thickness of 20 μm or less.
[4]
The method for producing Fe-Ni alloy foil according to any one of [1] to [3] above,
The ingredients are mass%,
C: 0 to 0.030%,
Si: 0 to 0.21%,
Mn: 0 to 0.30%,
Ni: 30.0 to 60.0%,
Co: 0-5.00%,
P: 0.01% or less,
A step of preparing Fe-Ni alloy powder in which S: 0.01% or less and the balance is Fe and impurities;
A Fe-Ni alloy ingot manufacturing step of manufacturing an Fe-Ni alloy ingot by the HIP method from the Fe-Ni alloy powder;
A method for producing Fe--Ni alloy foil, comprising a rolling step of rolling the Fe--Ni alloy ingot.
[5]
The method for producing an Fe--Ni alloy foil according to [4], further comprising at least one annealing step between each rolling pass of the rolling step or after the final rolling.
[6]
A component comprising the Fe-Ni alloy foil according to any one of [1] to [3] above.
　本発明によれば、耳波、中伸び、反りといった変形を抑制したＦｅ－Ｎｉ合金箔を得ることができる。 According to the present invention, it is possible to obtain an Fe--Ni alloy foil that suppresses deformations such as ear waves, mid-elongation, and warping.
Ｆｅ－Ｎｉ合金箔におけるＰＡＬと変形量の関係の一例を示す図である。FIG. 3 is a diagram showing an example of the relationship between PAL and deformation amount in Fe--Ni alloy foil. 鉛直方向吊り下げ試験の概要を示す図である。FIG. 3 is a diagram showing an outline of a vertical hanging test. 鉛直方向吊り下げ試験において、試験片と鉛直平面に生じた隙間の測定方法の一例を説明するための概念図である。FIG. 2 is a conceptual diagram for explaining an example of a method for measuring a gap created between a test piece and a vertical plane in a vertical hanging test.
　以下、本発明に係るＦｅ－Ｎｉ合金箔について詳述する。特に断りのない限り、成分に関する「％」は鋼中の質量％を示す。特に下限を規定していない場合や下限が０％の場合は含有しない場合（０％）を含む。 Hereinafter, the Fe-Ni alloy foil according to the present invention will be described in detail. Unless otherwise specified, "%" regarding components indicates mass % in steel. In particular, cases in which the lower limit is not specified or the lower limit is 0% include cases in which it is not contained (0%).
［陽子消滅寿命（ＰＡＬ）］
　陽電子消滅寿命（ＰＡＬ：Ｐｏｓｉｔｒｏｎ　Ａｎｎｉｈｉｌａｔｉｏｎ　Ｌｉｆｅｔｉｍｅ）は、金属材料や高分子材料などの材料中の空孔を含む格子欠陥の評価に用いられる指標である。平均陽電子消滅寿命と言う場合もある。ＰＡＬは、格子欠陥の種類を評価することができる。ＰＡＬは材料中の空孔数や空孔の大きさなどの総合的指標である。本発明での空孔とは、鋳造品における凝固時の収縮孔やガス空孔の類の欠陥ではなく、原子空孔や点欠陥を意味する。ＰＡＬについての詳細な説明は、ここでは割愛するが、空孔サイズが大きくなるほどＰＡＬが長くなる。一方、空孔の数が多くなるほど検出される相対強度（陽電子が消滅する際に放出するγ線のカウント数であり、存在確率に相当する。）が大きくなり、空孔数が多くなると空孔同士の結合が生じ、結果として空孔サイズも大きくなり、ＰＡＬが長くなる。 [Proton annihilation lifetime (PAL)]
Positron annihilation lifetime (PAL) is an index used to evaluate lattice defects including vacancies in materials such as metal materials and polymer materials. It is also sometimes referred to as the average positron annihilation lifetime. PAL can evaluate the type of lattice defects. PAL is a comprehensive index of the number of pores and the size of pores in a material. In the present invention, vacancies refer to atomic vacancies and point defects, rather than defects such as shrinkage pores or gas vacancies during solidification in cast products. A detailed explanation of the PAL will be omitted here, but the larger the pore size, the longer the PAL. On the other hand, as the number of vacancies increases, the detected relative intensity (the number of counts of γ rays emitted when a positron annihilates, which corresponds to the probability of existence) increases; As a result, the pore size also increases and the PAL becomes longer.
　陽電子消滅寿命（ＰＡＬ）はＰＡＬ測定装置により測定することができる。ＰＡＬ測定装置としては、例えばテクノエーピー社製の陽電子消滅寿命測定装置などの市販の装置が使用できる。発明者らは、テクノエーピー社製の陽電子消滅寿命測定装置で陽電子線源に２２Ｎａを用いて評価した。
　ＰＡＬ評価に際し、被評価材であるＦｅ－Ｎｉ合金箔を１０ｍｍ角に切断し、これを３枚重ねたものを２組準備し、陽電子線源を３枚重ねのＦｅ－Ｎｉ合金箔で挟み、これをアルミ箔で包み固定しＰＡＬ測定用試料を作成した。準備した測定用試料を測定装置にかけて陽電子消滅寿命（ＰＡＬ）を測定する。データ解析ソフトも測定装置に付属もの（例えばデンマーク工科大学が開発したＰＡＬＳｆｉｔ３）を使うとよい。測定に際してはカプトン膜の寿命（０．３８００ｐｓ）やエポキシ樹脂の寿命（１．９０４４ｐｓ）などの影響を考慮するため、これらの寿命を固定して解析するとよい。 Positron annihilation lifetime (PAL) can be measured with a PAL measuring device. As the PAL measuring device, a commercially available device such as a positron annihilation life measuring device manufactured by Techno-AP can be used. The inventors performed evaluation using a positron annihilation life measuring device manufactured by Techno-AP Co., Ltd. using 22 Na as a positron beam source.
For PAL evaluation, Fe-Ni alloy foil, which is the material to be evaluated, was cut into 10 mm squares, two sets of three stacked sheets were prepared, and the positron beam source was sandwiched between the three stacked Fe-Ni alloy foils. This was wrapped and fixed in aluminum foil to create a sample for PAL measurement. The prepared measurement sample is applied to a measuring device to measure the positron annihilation lifetime (PAL). It is also advisable to use the data analysis software that comes with the measuring device (for example, PALSfit3 developed by the Technical University of Denmark). In the measurement, in order to take into account the effects of the lifespan of the Kapton film (0.3800 ps), the lifespan of the epoxy resin (1.9044ps), etc., it is preferable to fix these lives for analysis.
　従来の溶製法で製造する材料（溶製材）は空孔が無いに等しく、格子欠陥の主体は転位である。さらに溶製材の場合、凝固過程において全体に均一に転位が導入されない。端的に言うと、凝固した合金塊の表面と中心部分では転位の状態が異なっている。欠陥の主体が転位である場合、加工に因る応力集中で降伏応力を超えると転位が発生し塑性変形することにより応力緩和するが、同時に転位どうしの相互作用により加工硬化する。従って、素材内に転位が不均一に導入された場合、局所的に応力緩和が発生し、残留応力が不均一になり易い。 Materials manufactured using conventional melting methods (melted materials) have virtually no pores, and the main lattice defects are dislocations. Furthermore, in the case of melt-sawn materials, dislocations are not uniformly introduced throughout the material during the solidification process. To put it simply, the state of dislocations is different between the surface and center of a solidified alloy lump. When the defects are mainly dislocations, when the stress concentration due to processing exceeds the yield stress, dislocations are generated and the stress is relaxed by plastic deformation, but at the same time work hardening occurs due to interactions between dislocations. Therefore, when dislocations are introduced non-uniformly into the material, stress relaxation occurs locally and residual stress tends to become non-uniform.
　一方、ＨＩＰ法などの熱間粉末冶金法では、収縮孔やガス空孔を消滅させることはできるが、原子空孔を消滅させることはできない。熱間粉末冶金法で製造される材料（熱間粉末冶金材）は、粉体を高温で等方的に圧縮、焼結するので、空孔が、素材内に一様に多数発生すると考えられる。熱間粉末冶金法ではこの空孔が拡散することにより、粒子間のネック部分を成長させ焼結が進行する。つまり、熱間粉末冶金法により製造された材料は、従来の溶製法による材料とは異なり空孔が存在するミクロ組織になっている。 On the other hand, hot powder metallurgy methods such as the HIP method can eliminate shrinkage pores and gas vacancies, but cannot eliminate atomic vacancies. Materials manufactured by hot powder metallurgy (hot powder metallurgy materials) are isotropically compressed and sintered at high temperatures, so it is thought that a large number of pores are uniformly generated within the material. . In the hot powder metallurgy method, the pores diffuse, causing neck portions between particles to grow and sintering to proceed. In other words, materials manufactured by hot powder metallurgy have a microstructure in which pores are present, unlike materials manufactured by conventional melting methods.
　空孔は刃状転位の上昇運動に使用され、また空孔が配列することにより転位を形成する役割がある。従って、陽電子消滅寿命が長く空孔の割合が大きな（量が多い）熱間粉末冶金材の組織は、空孔が移動し転位を形成しやすく、転位が多くの空孔を吸収しながら移動できるため、比較的転位が動きやすい組織になっていると考えられる。このような転位の形成し易さや動き易さは、材料の応力緩和に影響する。また転位に使われない残存空孔は固溶強化と同様に作用し基底強度に寄与する。従って、素材内に一様に空孔が導入されれば、圧延などで空孔が移動し易く、そのため比較的軽度の圧延負荷でも変形し易くなる。また素材内で一様に応力緩和がされ残留応力が均一になるため、変形（反りや横曲がり等）を抑制できると考えられる。一方、溶製材は陽電子消滅寿命が短く空孔の割合が小さい（量が少ない）為、刃状転位は上昇運動しにくく、転位は動きにくい。つまり溶製材は不均一に転位が分布し、さらに動きにくいため、残留応力が不均一に生じ形状不良が生じやすい。 The vacancies are used for the upward movement of edge dislocations, and the arrangement of the vacancies plays a role in forming dislocations. Therefore, in the structure of a hot powder metallurgy material with a long positron annihilation life and a large proportion (large amount) of vacancies, vacancies move easily and form dislocations, and dislocations can move while absorbing many vacancies. Therefore, it is thought that the structure has a relatively easy movement of dislocations. The ease with which such dislocations form and move affects the stress relaxation of the material. In addition, the remaining vacancies that are not used for dislocations act similarly to solid solution strengthening and contribute to the basic strength. Therefore, if pores are uniformly introduced into the material, the pores are likely to move during rolling or the like, and therefore become easily deformed even under a relatively light rolling load. Furthermore, since stress is uniformly relaxed within the material and residual stress becomes uniform, it is thought that deformation (warping, lateral bending, etc.) can be suppressed. On the other hand, melt-molded materials have a short positron annihilation life and a small proportion (amount) of vacancies, so edge dislocations are difficult to move upward, and dislocations are difficult to move. In other words, dislocations are distributed non-uniformly in melt-sawn material and it is difficult to move, so residual stress is non-uniform and shape defects are likely to occur.
　本発明者らが実験により確認したところ、従来の溶製材であればＰＡＬが０．１５０ｎｓ以上になることはないが、熱間粉末冶金材であれば０．１５０ｎｓ以上になることを確認した。即ち、従来の溶製材のように欠陥が転位主体の素材の場合はＰＡＬが０．１５０ｎｓ未満であり、熱間粉末冶金材のような空孔などの点欠陥が主体の素材の場合はＰＡＬが０．１５０ｎｓ以上になることを確認した。よって、ＰＡＬが０．１５０ｎｓ以上であるということは、格子欠陥が空孔などの点欠陥主体である組織であることを示していると考えられる。即ち、ＰＡＬ０．１５０ｎｓが、転位主体から空孔主体のミクロ組織に変わる境界になるものと考えられる。 As a result of experiments conducted by the present inventors, it was confirmed that the PAL of conventional melt-molded materials does not exceed 0.150 ns, but the PAL of hot powder metallurgy materials exceeds 0.150 ns. That is, in the case of a material whose defects are mainly dislocations, such as conventional melt-molded materials, the PAL is less than 0.150 ns, and in the case of materials whose defects are mainly point defects such as pores, such as hot powder metallurgy materials, the PAL is less than 0.150 ns. It was confirmed that the time was 0.150 ns or more. Therefore, it is considered that the PAL of 0.150 ns or more indicates that the lattice defects are mainly point defects such as vacancies. That is, it is considered that PAL 0.150 ns is the boundary at which the microstructure changes from a dislocation-based microstructure to a vacancy-based microstructure.
［変形量］
　Ｆｅ－Ｎｉ合金箔の耳波、中伸び、反りなどの変形は、複合的に発生するため、それぞれの変形を個別に評価することは難しい。そこで、合金箔の変形を総合的に評価するため、合金箔を鉛直に吊り下げた際に、合金箔の鉛直方向に対する変形量の最大値をもって、合金箔の変形量として評価できると考えた。 [Deformation amount]
Deformations of Fe--Ni alloy foil, such as ear waves, mid-elongation, and warping, occur in a complex manner, so it is difficult to evaluate each deformation individually. Therefore, in order to comprehensively evaluate the deformation of the alloy foil, we thought that when the alloy foil is suspended vertically, the maximum value of the amount of deformation of the alloy foil in the vertical direction can be evaluated as the amount of deformation of the alloy foil.
　本発明者らは、鉛直方向吊り下げ試験による変形量評価のため、次の試験方法を採用した。即ち、合金箔を例えば幅４０ｍｍ、長さ２５０ｍｍの短冊状に切断したものを試験片とし、これを鉛直定盤（鉛直方向に平行な平面（鉛直平面）を有する定盤）に吊り下げ、鉛直平面と試験片の間の隙間量を実測し、その最大値を以って変形量として評価するとよい。通常、耳波、中伸びは圧延方向に沿って生じるため、試験片の長辺を圧延方向にするとよい。また、合金箔を製造する際にコイル状に巻き取る場合があり、その際生じる巻取り癖を解消するため、一定の張力を付加するとよい。例えば、厚さ５０μｍ以下で幅４０ｍｍの試験片であれば１００ｇの重りを試験片下方端に付けて張力を発生させるとよい。試験片と鉛直平面の隙間の測定方法は特に限定されないが、隙間ゲージやレーザー測長、写真撮影による画像解析などで計測することができる。 The present inventors adopted the following test method to evaluate the amount of deformation by a vertical hanging test. That is, a test piece is prepared by cutting an alloy foil into strips with a width of 40 mm and a length of 250 mm, and this is hung on a vertical surface plate (a surface plate having a plane parallel to the vertical direction (vertical plane)). It is preferable to actually measure the amount of gap between the plane and the test piece, and evaluate the amount of deformation using the maximum value. Since ear waves and mid-elongation usually occur along the rolling direction, it is preferable to set the long side of the test piece in the rolling direction. Further, when manufacturing alloy foil, it may be wound into a coil shape, and in order to eliminate the winding tendency that occurs at that time, it is recommended to apply a certain tension. For example, if the test piece is 50 μm or less thick and 40 mm wide, a 100 g weight may be attached to the lower end of the test piece to generate tension. The method for measuring the gap between the test piece and the vertical plane is not particularly limited, but it can be measured using a gap gauge, laser length measurement, image analysis using photography, or the like.
［陽子消滅寿命（ＰＡＬ）≧０．１５０ｎｓ］
　図１に、実施例にて示すＦｅ－Ｎｉ合金箔によるＰＡＬと変形量の関係の一例を示す。図１は、厚さ３０μｍのＦｅ－Ｎｉ合金箔によりＰＡＬと変形量の関係を示したものである。図１に示すように、変形量とＰＡＬは強い相関関係にあり、ＰＡＬが長くなると変形量が減少することが確認された。即ち、格子欠陥の種類を転位主体（ＰＡＬが０．１５０ｎｓ未満）から空孔主体（ＰＡＬが０．１５０ｎｓ以上）の組織にすることにより、合金箔の変形を抑制できることが確認された。 [Proton annihilation lifetime (PAL) ≧0.150ns]
FIG. 1 shows an example of the relationship between PAL and deformation amount using Fe--Ni alloy foil shown in Examples. FIG. 1 shows the relationship between PAL and deformation amount using a 30 μm thick Fe-Ni alloy foil. As shown in FIG. 1, it was confirmed that there is a strong correlation between the amount of deformation and PAL, and that the amount of deformation decreases as PAL becomes longer. That is, it was confirmed that the deformation of the alloy foil could be suppressed by changing the type of lattice defects from a structure mainly composed of dislocations (PAL of less than 0.150 ns) to a structure mainly composed of vacancies (PAL of 0.150 ns or more).
　即ち、ＰＡＬを０．１５０ｎｓ以上にすることにより、空孔主体のミクロ組織のＦｅ－Ｎｉ合金が得られ、圧延による残留応力の不均一性が軽減され、結果として変形量が抑制されたＦｅ－Ｎｉ合金箔が得られることが確認された。ＰＡＬが長いほど変形量が小さくなることから、ＰＡＬは長い方が好ましい。従って、ＰＡＬの下限は、好ましくは０．１５１ｎｓ、０．１５２ｎｓ、０．１５３ｎｓ、０．１５４ｎｓ、０．１５５ｎｓ、０．１５６ｎｓ、０．１５７ｎｓ、０．１５８ｎｓ、０．１５９ｎｓ、０．１６０ｎｓ、０．１６１ｎｓ、０．１６２ｎｓ、０．１６３ｎｓ、０．１６４ｎｓ、または０．１６５ｎｓであるとよい。 That is, by setting the PAL to 0.150 ns or more, an Fe-Ni alloy with a microstructure consisting mainly of pores can be obtained, the non-uniformity of residual stress due to rolling is reduced, and as a result, the amount of deformation is suppressed in the Fe-Ni alloy. It was confirmed that Ni alloy foil was obtained. Since the longer the PAL, the smaller the amount of deformation, the longer the PAL is, the better. Therefore, the lower limit of PAL is preferably 0.151ns, 0.152ns, 0.153ns, 0.154ns, 0.155ns, 0.156ns, 0.157ns, 0.158ns, 0.159ns, 0.160ns, 0 The length may be .161ns, 0.162ns, 0.163ns, 0.164ns, or 0.165ns.
　一方、ＰＡＬが長くなるほど変形量は小さくなる。しかし、ある程度ＰＡＬが長くなると大きな空孔が存在することになり、その大きな空孔が破壊の起点になる恐れがある。本発明者らの実験から、実用的な熱間粉末冶金材でのＰＡＬ実測値は０．２００ｎｓを超えるものはなかった。従って、ＰＡＬの上限値は特に限定する必要はないものの、上限値を設定する場合は０．２００ｎｓ、好ましくは０．１９８ｎｓ、０．１９６ｎｓ、０．１９４ｎｓ、０．１９２ｎｓ、０．１９０ｎｓ、０．１８８ｎｓ、０．１８６ｎｓ、０．１８４ｎｓ、０．１８２ｎｓ、または０．１８０ｎｓにするとよい。 On the other hand, the longer the PAL, the smaller the amount of deformation. However, if the PAL becomes long to a certain extent, large pores will be present, and there is a possibility that the large pores will become the starting point of destruction. From experiments conducted by the present inventors, there were no actual PAL values exceeding 0.200 ns for practical hot powder metallurgy materials. Therefore, although there is no need to specifically limit the upper limit value of PAL, when setting the upper limit value, it is 0.200 ns, preferably 0.198 ns, 0.196 ns, 0.194 ns, 0.192 ns, 0.190 ns, 0. It is preferable to set it to 188ns, 0.186ns, 0.184ns, 0.182ns, or 0.180ns.
［Ｆｅ－Ｎｉ合金箔の成分］
　Ｆｅ－Ｎｉ合金箔の成分について説明する。前述したように、特に断りのない限り、成分に関する「％」は鋼中の質量％を示す。特に下限を規定していない場合や下限が０％の場合は含有しない場合（０％）を含む。 [Components of Fe-Ni alloy foil]
The components of the Fe-Ni alloy foil will be explained. As mentioned above, unless otherwise specified, "%" regarding components indicates mass % in the steel. In particular, cases in which the lower limit is not specified or the lower limit is 0% include cases in which it is not contained (0%).
Ｃ　：０～０．０３０％、
　炭素（Ｃ）は、合金箔の強度を高める。しかしながら、Ｃが過剰に含有されれば、合金の炭化物由来の介在物が増加する。従って、Ｃ含有量は０．０３０％以下にするとよい。好ましくは、０．０２８％、０．０２６％、０．０２４％、０．０２２％、または０．０２０％にするとよい。 C: 0 to 0.030%,
Carbon (C) increases the strength of the alloy foil. However, if C is contained excessively, inclusions derived from carbides in the alloy increase. Therefore, the C content is preferably 0.030% or less. Preferably, it is 0.028%, 0.026%, 0.024%, 0.022%, or 0.020%.
Ｓｉ：０～０．２１％
　珪素（Ｓｉ）は合金の熱膨張係数を増加させる。Ｆｅ－Ｎｉ合金箔は、もともと低熱膨張係数であることを期待される合金であり、その用途にもよるが、２００℃程度の温度環境下で使用される場合がある。さらに、Ｓｉ含有量が多過ぎると強度が高くなり過ぎ、合金の加工性が低下する。そのため、熱膨張を抑制する観点や加工性の観点からＳｉ含有量は０．２１％以下にするとよい。好ましくは、０．２０％以下、０．１８％以下、０．１６％、０．１４％、０．１２％、または０．１０％以下にするとよい。 Si: 0-0.21%
Silicon (Si) increases the coefficient of thermal expansion of the alloy. Fe--Ni alloy foil is an alloy that is originally expected to have a low coefficient of thermal expansion, and may be used in a temperature environment of about 200° C., depending on its use. Furthermore, if the Si content is too high, the strength will become too high and the workability of the alloy will decrease. Therefore, from the viewpoint of suppressing thermal expansion and workability, the Si content is preferably 0.21% or less. Preferably, it is 0.20% or less, 0.18% or less, 0.16%, 0.14%, 0.12%, or 0.10% or less.
Ｍｎ：０～０．３０％、
　マンガン（Ｍｎ）は、スピネルの生成を避けるため、ＭｇおよびＡｌの代わりに脱酸剤として用いられる。しかし、Ｍｎ含有量が高すぎれば、粒界に偏析して粒界破壊を助長して、耐水素脆化性がかえって悪くなるので、Ｍｎ含有量は、０．３０％以下にするとよい。Ｍｎ含有量の好ましい範囲は０．２８％以下、０．２６％以下、０．２４％以下、０．２２％以下、０．２０％以下、０．１８％以下、または０．１６％以下にするとよい。 Mn: 0 to 0.30%,
Manganese (Mn) is used as a deoxidizer instead of Mg and Al to avoid spinel formation. However, if the Mn content is too high, it will segregate at grain boundaries and promote intergranular fracture, resulting in poor hydrogen embrittlement resistance, so the Mn content is preferably 0.30% or less. The preferred range of Mn content is 0.28% or less, 0.26% or less, 0.24% or less, 0.22% or less, 0.20% or less, 0.18% or less, or 0.16% or less. It's good to do that.
Ｎｉ：３０．０～６０．０％、
　ニッケル（Ｎｉ）は合金の熱膨張係数を低く抑えるための主要成分であり、且つＮｉ含有量が低すぎれば、体心立方（ｂｃｃ）構造が増加し、転位の挙動が変化するためＮｉ含有量を３０．０％以上にするとよい。一方、Ｎｉ含有量が高すぎれば、熱間加工（熱間圧延や熱間鍛造）後において、合金中にベイナイト組織が生成しやすくなる。従って、Ｎｉ含有量は６０．０％以下にするとよい。Ｎｉ含有量の好ましい範囲は、下限側では３１．０％以上、３１．５％以上、３２．０％以上、３２．５％以上、３３．０％以上、３３．５％以上、３４．０％以上、３４．５％以上、３５．０％以上、３５．２％以上、または３５．４％以上にするとよく、上限側では５９．０％以下、５８．０％以下、５７．０％以下、５６．０％以下、５５．０％以下、５４．０％以下、５３．０％以下、５２．０％以下、５１．０％以下、５０．０％以下、４９．０％以下、４８．０％以下、４７．０％以下、４６．０％以下、４５．０％以下、４４．０％以下、４３．０％以下、４２．０％以下、４１．０％以下、４０．０％以下、３９．５％以下、３９．０％以下、３８．５％以下、３８．０％以下、３７．５％以下、または３７．０％以下にするとよい。 Ni: 30.0 to 60.0%,
Nickel (Ni) is a main component that keeps the coefficient of thermal expansion of the alloy low, and if the Ni content is too low, the body-centered cubic (BCC) structure will increase and the behavior of dislocations will change. is preferably 30.0% or more. On the other hand, if the Ni content is too high, a bainite structure is likely to be generated in the alloy after hot working (hot rolling or hot forging). Therefore, the Ni content is preferably 60.0% or less. The preferable range of Ni content is 31.0% or more, 31.5% or more, 32.0% or more, 32.5% or more, 33.0% or more, 33.5% or more, 34.0 on the lower limit side. % or more, 34.5% or more, 35.0% or more, 35.2% or more, or 35.4% or more, and on the upper limit side, 59.0% or less, 58.0% or less, 57.0% Below, 56.0% or less, 55.0% or less, 54.0% or less, 53.0% or less, 52.0% or less, 51.0% or less, 50.0% or less, 49.0% or less, 48.0% or less, 47.0% or less, 46.0% or less, 45.0% or less, 44.0% or less, 43.0% or less, 42.0% or less, 41.0% or less, 40. It is preferably 0% or less, 39.5% or less, 39.0% or less, 38.5% or less, 38.0% or less, 37.5% or less, or 37.0% or less.
Ｃｏ：０～５．００％、
　Ｎｉ量との関連でその添加量を増していくと合金の熱膨張係数を一段と低下させることができる成分である。しかし、非常に価格の高い元素であるためＣｏ含有量の上限を ５．００％とするとよい。好ましくは４．５０％以下、４．００％以下、３．５０％以下、３．００％以下、２．５０％以下、２．００％以下、１．５０％以下、または１．００％以下にするとよい。 Co: 0-5.00%,
It is a component that can further reduce the coefficient of thermal expansion of the alloy as its addition amount increases in relation to the amount of Ni. However, since Co is a very expensive element, it is preferable to set the upper limit of the Co content to 5.00%. Preferably 4.50% or less, 4.00% or less, 3.50% or less, 3.00% or less, 2.50% or less, 2.00% or less, 1.50% or less, or 1.00% or less It is better to make it .
　［不純物］
　上記の元素の他、残部はＦｅ（鉄）および不純物である。不純物とは、製造する過程で意図せずに含有される元素のことである。特に、不純物として、Ｐ、Ｓ等の成分が挙げられる。ＰやＳの含有量は、以下の範囲内に制限されることが好ましい。 [impurities]
In addition to the above elements, the remainder is Fe (iron) and impurities. Impurities are elements that are unintentionally included during the manufacturing process. In particular, impurities include components such as P and S. It is preferable that the content of P and S is limited within the following range.
Ｐ　：０．０１０％以下、
　Ｐは凝固時に粒界に偏析し、凝固割れ感受性を高める。従って、Ｐ含有量はできるだけ低い方が好ましい。そのため、Ｐ含有量は０．０１０％以下に制限する。好ましくは０．００５％以下、または０．００３％以下にするとよい。Ｐ含有量の下限は０％であるが、過剰に低下させることは製造コストを上昇させるため、現実的には０．００１％以上であってもよい。 P: 0.010% or less,
P segregates at grain boundaries during solidification and increases susceptibility to solidification cracking. Therefore, it is preferable that the P content be as low as possible. Therefore, the P content is limited to 0.010% or less. The content is preferably 0.005% or less, or 0.003% or less. Although the lower limit of the P content is 0%, in reality it may be 0.001% or more, since reducing it excessively increases manufacturing costs.
Ｓ　：０．０１０％以下、
　Ｓは凝固時に粒界に偏析し、凝固割れ感受性を高める。従って、Ｓ含有量はできるだけ低い方が好ましい。そのため、Ｓ含有量は０．０１０％以下に制限する。好ましくは、０．００５％以下、または０．００２％以下にするとよい。Ｓ含有量の下限は０％であるが、過剰に低下させることは製造コストを上昇させるため、現実的には０．００１％以上であってもよい。 S: 0.010% or less,
S segregates at grain boundaries during solidification and increases susceptibility to solidification cracking. Therefore, it is preferable that the S content be as low as possible. Therefore, the S content is limited to 0.010% or less. Preferably, it is 0.005% or less, or 0.002% or less. Although the lower limit of the S content is 0%, in reality it may be 0.001% or more, since reducing it excessively increases manufacturing costs.
　不純物として、本発明の効果を損なわない範囲であれば、その他の元素も不純物として含有してもよい。例えば、Ｃｒ、Ａｌ、Ｃｕ、Ｎｂ、Ｍｏ、Ｔｉ、Ｍｇ、Ｃａ、Ｓｎ、Ｖ、Ｗ、Ｚｒ、Ｂ、Ｂｉなどが挙げられる。 Other elements may also be contained as impurities as long as they do not impair the effects of the present invention. Examples include Cr, Al, Cu, Nb, Mo, Ti, Mg, Ca, Sn, V, W, Zr, B, Bi, and the like.
［板厚］
　Ｆｅ－Ｎｉ合金箔の板厚は特に限定されない。板厚１００μｍ以下の合金板を合金箔と呼んでいるが、板厚１００μｍ以上の合金板に適用してもよい。しかし、一般に板厚が薄くなるほど耳波、中伸び、反りなどの変形が発生し易くなる。そのため、板厚５０μｍ以下のＦｅ－Ｎｉ合金箔に本発明を適用するとより効果的である。板厚は薄いほど、本発明の効果を享受することができるので、好ましくは４５μｍ以下、４０μｍ以下、３５μｍ以下、３０μｍ以下、２５μｍ以下、２０μｍ以下、１５μｍ以下、１０μｍ以下、または５μｍ以下であるとよい。板厚の下限は特に限定されないが、工業的製造可能性の観点から板厚１．０μｍ以上であってもよい。 [Plate thickness]
The thickness of the Fe--Ni alloy foil is not particularly limited. Although an alloy plate with a thickness of 100 μm or less is called an alloy foil, it may also be applied to an alloy plate with a thickness of 100 μm or more. However, in general, the thinner the plate, the more likely deformations such as ear waves, elongation, and warping occur. Therefore, it is more effective to apply the present invention to Fe--Ni alloy foil with a thickness of 50 μm or less. The thinner the plate thickness is, the more the effects of the present invention can be enjoyed, so it is preferably 45 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, or 5 μm or less. good. Although the lower limit of the plate thickness is not particularly limited, the plate thickness may be 1.0 μm or more from the viewpoint of industrial manufacturability.
［製造方法］
　本発明に係るＦｅ－Ｎｉ合金箔の製造方法は特に限定されない。しかし、主に合金塊の製造工程、圧延工程、焼鈍工程において工夫することによりＰＡＬを長寿命化することができる。以下にその方法について説明する。なお、本発明に係るＦｅ－Ｎｉ合金箔はここに記載される製造方法に限定されることはない。 [Production method]
The method for manufacturing the Fe--Ni alloy foil according to the present invention is not particularly limited. However, the life of PAL can be extended by making improvements mainly in the manufacturing process, rolling process, and annealing process of the alloy ingot. The method will be explained below. Note that the Fe--Ni alloy foil according to the present invention is not limited to the manufacturing method described herein.
［Ｆｅ－Ｎｉ合金塊製造工程］
　Ｆｅ－Ｎｉ合金塊の製造工程とは、所定の成分組成を有するＦｅ－Ｎｉ合金の塊（鋼片、スラブなど）を得る工程である。例えば、溶融したＦｅ－Ｎｉ合金を精錬して凝固させる方法、いわゆる溶製方法がある。また例えば、所定の成分組成の金属粉を組み合わせ、ＨＩＰ（Ｈｏｔ　Ｉｓｏｓｔａｔｉｃ　Ｐｒｅｓｓ）などのように高温高圧下で固相接合させる方法、いわゆる熱間粉末冶金法などがある。 [Fe-Ni alloy ingot manufacturing process]
The manufacturing process of an Fe-Ni alloy ingot is a process of obtaining a Fe-Ni alloy ingot (steel billet, slab, etc.) having a predetermined composition. For example, there is a method of refining and solidifying a molten Fe--Ni alloy, a so-called melting method. Further, for example, there is a method in which metal powders having a predetermined composition are combined and solid phase bonded under high temperature and high pressure such as HIP (Hot Isostatic Press), a so-called hot powder metallurgy method.
　前述したように、従来の溶製法で製造する溶製材の合金塊（溶製合金塊）は空孔が無いに等しく、格子欠陥の主体は転位である。さらに溶製材の場合、凝固過程において全体に均一に転位が導入されない。端的に言うと、溶製合金塊の表面と中心部分では転位の導入の仕方が異なっている。欠陥の主体が転位である場合、加工に因る応力集中で降伏応力を超えると転位が発生し塑性変形することにより応力緩和する。従って、溶製合金は、素材内に転位が不均一に導入された場合、局所的に応力緩和が発生し、残留応力が不均一に生じ易い。 As mentioned above, the alloy ingot of ingot material (ingot alloy ingot) produced by the conventional ingot manufacturing method has almost no pores, and the main lattice defects are dislocations. Furthermore, in the case of melt-sawn materials, dislocations are not uniformly introduced throughout the material during the solidification process. To put it simply, the way in which dislocations are introduced is different between the surface and the center of a melted alloy ingot. When the main defect is dislocation, when the stress concentration due to processing exceeds the yield stress, dislocation occurs and the stress is relaxed by plastic deformation. Therefore, when dislocations are non-uniformly introduced into the material of a melt-produced alloy, stress relaxation occurs locally, and residual stress tends to occur non-uniformly.
　一方、ＨＩＰ法などの熱間粉末冶金法では、収縮孔やガス空孔を消滅させることはできるが、原子空孔を消滅させることは不可能である。熱間粉末冶金法で製造される材料（熱間粉末冶金材）は、粉体を高温で等方的に圧縮、焼結するので、空孔が、素材内に一様に多数発生すると考えられる。熱間粉末冶金法ではこの空孔が拡散することにより、粒子間のネック部分を成長させ焼結が進行する。つまり、熱間粉末冶金法により製造された材料は、溶製材とは異なり空孔が存在するミクロ組織である。従って、ＨＩＰ法などの熱間粉末冶金法の方が、従来の溶製法に比べ空孔が一様に多数発生し、ＰＡＬが長寿命化した合金塊を得ることができる。 On the other hand, in hot powder metallurgy methods such as the HIP method, shrinkage pores and gas vacancies can be eliminated, but atomic vacancies cannot be eliminated. Materials manufactured by hot powder metallurgy (hot powder metallurgy materials) are isotropically compressed and sintered at high temperatures, so it is thought that a large number of pores are uniformly generated within the material. . In the hot powder metallurgy method, the pores diffuse, causing neck portions between particles to grow and sintering to proceed. In other words, a material manufactured by hot powder metallurgy has a microstructure in which pores are present, unlike ingot material. Therefore, a hot powder metallurgy method such as the HIP method can produce an alloy ingot with a uniformly larger number of pores and a longer PAL life than the conventional melting method.
［Ｆｅ－Ｎｉ合金粉末準備工程］
　熱間粉末冶金法で製造する場合、その製造方法は特に限定されない。例えば、従来用いられているＨＩＰ方法を適用することができる。製造される合金塊中の空孔を一様に発生させるため、ＨＩＰ法の原料なる金属粉末は微細粒である方が好ましい。例えば、金属粉末の粒径を５００μｍ以下、４００μｍ以下、３００μｍ以下、２００μｍ以下、または１００μｍ以下にするとよい。金属粉末の製造方法も特に限定されない。従来の精錬法により所定の成分組成に調整した溶湯を、アトマイズ法などを適用して合金粉末を得ることができる。このときの精錬法も特に限定されない。実験室レベルでは、真空誘導加熱炉で行うこともできる。炭素量、ガス成分、金属介在物を低減するために、ＡＯＤ（Argon-Oxygen-Decarburization）法、ＶＯＤ（Vacuum-Oxygen-Decarburization）法、Ｖ－ＡＯＤ法等が適用可能である。 [Fe-Ni alloy powder preparation process]
When manufacturing by hot powder metallurgy, the manufacturing method is not particularly limited. For example, a conventionally used HIP method can be applied. In order to uniformly generate pores in the manufactured alloy ingot, it is preferable that the metal powder used as the raw material for the HIP method is finely grained. For example, the particle size of the metal powder is preferably 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, or 100 μm or less. The method for producing metal powder is also not particularly limited. An alloy powder can be obtained by applying an atomization method or the like to a molten metal that has been adjusted to a predetermined composition using a conventional refining method. The refining method at this time is also not particularly limited. At the laboratory level, it can also be carried out in a vacuum induction furnace. In order to reduce the amount of carbon, gas components, and metal inclusions, AOD (Argon-Oxygen-Decarburization) method, VOD (Vacuum-Oxygen-Decarburization) method, V-AOD method, etc. can be applied.
　準備した合金粉末を金属容器に入れＨＩＰ処理することにより所望の合金塊を得ることができる。ＨＩＰなどの熱間粉末冶金法であれば、最終製品形状に近いニアーネットシェイプな合金塊を得ることができ、その後の加工工程（圧延や鍛造などの加工）を省略化することができる。 A desired alloy ingot can be obtained by placing the prepared alloy powder in a metal container and subjecting it to HIP treatment. With hot powder metallurgy such as HIP, it is possible to obtain an alloy ingot with a near-net shape close to the shape of the final product, and subsequent processing steps (processing such as rolling and forging) can be omitted.
［圧延工程］
　得られたＦｅ－Ｎｉ合金塊を熱間圧延や冷間圧延することにより合金箔を得ることができる。一般的には、Ｆｅ－Ｎｉ合金塊を熱間圧延し厚さ１ｍｍ以下のＦｅ－Ｎｉ合金板にした後、冷間圧延により所望の板厚の合金箔を得ることができる。熱間圧延も冷間圧延も従来の製造方法を採用することができる。しかし、ＰＡＬを長寿命化するためには、冷間圧延の各パスの合計圧下率が大きすぎない方が好ましい。冷間圧延の合計圧下率が大きすぎると圧延により歪が蓄積された高転位密度の圧延組織となり空孔が消費され易くなるためである。加工硬化能が低下しない範囲で、冷間圧延の合計圧下率を下げたマイルドな圧延になるようなプロセス設計が好ましい。 [Rolling process]
An alloy foil can be obtained by hot rolling or cold rolling the obtained Fe--Ni alloy ingot. Generally, an Fe--Ni alloy ingot can be hot-rolled into a Fe--Ni alloy plate with a thickness of 1 mm or less, and then cold-rolled to obtain an alloy foil with a desired thickness. Conventional manufacturing methods can be used for both hot rolling and cold rolling. However, in order to extend the life of PAL, it is preferable that the total reduction ratio of each pass of cold rolling is not too large. This is because if the total reduction ratio of cold rolling is too large, a rolled structure with a high dislocation density in which strain is accumulated due to rolling is formed, and pores are likely to be consumed. It is preferable to design a process that allows for mild rolling with a lower total cold rolling reduction within a range that does not reduce the work hardening ability.
［焼鈍工程］
　Ｆｅ－Ｎｉ合金箔を製造する場合、板厚が薄くなると（例えば板厚１００μｍ以下）圧延工程（特に冷間圧延）の圧延パス間（各圧延パス間であってもよく、数パスの間であってもよい。）または最終圧延後に少なくとも１回の焼鈍（圧延パス間は中間焼鈍、最終圧延後は最終焼鈍と呼ぶ。）を施すとよい。焼鈍を行うと、転位、空孔共に一旦減少し均一な再結晶組織が形成される。中間焼鈍の場合、その後の圧延により再度転位が導入されるが、未焼鈍の圧延組織に比べて転位密度は高くないため、転位は動きやすく、転位の切り合いによって、空孔が生じながら転位密度も増大する。結果としてＰＡＬの長寿命化につながる。従って、焼鈍は行った方が好ましく、特に圧延間の中間焼鈍は行った方が好ましい。 [Annealing process]
When manufacturing Fe-Ni alloy foil, when the plate thickness becomes thin (for example, plate thickness 100 μm or less), the rolling process (especially cold rolling) may occur between rolling passes (may be between each rolling pass, or between several passes). ) or at least one annealing after the final rolling (the period between rolling passes is called an intermediate annealing, and the period after the final rolling is called a final annealing). When annealing is performed, both dislocations and vacancies are temporarily reduced and a uniform recrystallized structure is formed. In the case of intermediate annealing, dislocations are reintroduced by subsequent rolling, but the dislocation density is not as high as in the unannealed rolled structure, so the dislocations are easy to move, and the dislocations cut together, creating vacancies and increasing the dislocation density. also increases. As a result, the life of PAL is extended. Therefore, it is preferable to perform annealing, and it is particularly preferable to perform intermediate annealing between rolling.
　上記したように焼鈍により転位を消滅させるとよいが、再結晶を伴わない場合転位の消滅は進まない。そのため、できるだけ再結晶温度以上の焼鈍を行うことが望ましい。例えばＦｅ－Ｎｉ合金やステンレス鋼の場合は７００℃以上の温度で焼鈍することが好ましい。好ましくは、７５０℃以上、または８００℃以上にするとよい。７００℃未満の焼鈍では転位が残存した状態で圧延するため、最終圧延で転位が導入され易く圧延負荷は小さくなるが、高転位密度状態になり空孔が消費され易くなり、結果としてＰＡＬが短寿命化する。 As mentioned above, it is preferable to eliminate dislocations by annealing, but dislocations will not disappear if recrystallization is not involved. Therefore, it is desirable to perform annealing at a temperature higher than the recrystallization temperature as much as possible. For example, in the case of Fe-Ni alloy or stainless steel, it is preferable to anneal at a temperature of 700° C. or higher. Preferably, the temperature is 750°C or higher, or 800°C or higher. When annealing at a temperature lower than 700°C, rolling is performed with dislocations remaining, so dislocations are easily introduced in the final rolling and the rolling load is reduced, but the dislocation density becomes high and vacancies are easily consumed, resulting in a short PAL. Increase lifespan.
［部品材料への適用］
　なお、本発明に係るＦｅ－Ｎｉ合金箔は、薄厚化しても変形が抑制されていることから、あらゆる部品の材料として適用することができる。特に、電池材料などの電子機器では、軽量化と高機能化、高強度化のニーズから薄厚合金箔の要求が高まっており、これらの部品材料に適用することが好ましい。 [Application to parts materials]
Note that the Fe--Ni alloy foil according to the present invention can be used as a material for all kinds of parts, since deformation is suppressed even when the foil is thinned. In particular, in electronic devices such as battery materials, there is an increasing demand for thin alloy foils due to the need for lighter weight, higher functionality, and higher strength, and it is preferable to apply them to these component materials.
　また、部品そのものに適用しないものの、部品製造時に使用する部品（部材）にも適用することができる。例えば、ＯＬＥＤのメタルマスクに本発明に係るＦｅ－Ｎｉ合金箔を適用するとよい。ＯＬＥＤのメタルマスクは、高精細化のためエッチング性と低熱膨張性からＦｅ－Ｎｉ合金箔が適用されているが、さらなる高精細化のため薄厚化と変形量の抑制が求められているからである。 Furthermore, although it is not applied to the parts themselves, it can also be applied to parts (members) used when manufacturing parts. For example, the Fe--Ni alloy foil according to the present invention may be applied to a metal mask of an OLED. Fe-Ni alloy foil is used for OLED metal masks due to its etchability and low thermal expansion properties to achieve higher definition. be.
　メタルマスクのように電子部品や機械部品そのものではなく、電子部品を製造するために使用する部品（部材）も、本発明において部品に含める。 In the present invention, parts (members) used to manufacture electronic parts, such as metal masks, rather than electronic parts or mechanical parts themselves, are also included in parts.
　また、本発明に係るＦｅ－Ｎｉ合金箔を有する部品とは、部品がＦｅ－Ｎｉ合金箔から製造されたものだけではなく、Ｆｅ－Ｎｉ合金箔からなる部分を有する場合も含む。 Furthermore, the parts having Fe-Ni alloy foil according to the present invention include not only parts manufactured from Fe-Ni alloy foil but also parts having parts made of Fe-Ni alloy foil.
［試験材］
　Ｆｅ－３６Ｎｉ合金をベースにして表１に示す成分組成に調整したＦｅ－Ｎｉ合金塊をＨＩＰ法によるＨＩＰ材、および従来製法に準拠した溶製材を準備した。なお、表１の成分の残部はＦｅおよび不純物である。 [Test material]
A Fe-Ni alloy ingot based on Fe-36Ni alloy and adjusted to the composition shown in Table 1 was prepared as a HIP material by the HIP method and as a melt-molten material in accordance with a conventional manufacturing method. Note that the remainder of the components in Table 1 are Fe and impurities.
　まず、ＨＩＰ材については、表１に示す成分組成に調整した溶湯（溶融合金）をガスアトマイズ法により球状の合金粉にした。得られた合金粉を分級し、３００μｍの篩下品をＨＩＰ処理して、ＨＩＰ材を得た。ＨＩＰ処理は通常の手順で行い、ＨＩＰ処理条件として１１５０℃、１２０ＭＰａの高温高圧下で３時間保持してＨＩＰ材を製造した。表１に示すように、成分の異なるＨＩＰ材としてＨＩＰ１とＨＩＰ２を準備した。 First, for the HIP material, molten metal (molten alloy) adjusted to the composition shown in Table 1 was made into spherical alloy powder by gas atomization. The obtained alloy powder was classified, and the 300 μm unsieved product was subjected to HIP treatment to obtain a HIP material. The HIP treatment was carried out according to the usual procedure, and the HIP material was manufactured by holding the HIP treatment at a high temperature and pressure of 1150° C. and 120 MPa for 3 hours. As shown in Table 1, HIP1 and HIP2 were prepared as HIP materials with different components.
　一方、比較材として従来製法に準拠した連鋳スラブ材は、表１に示す成分組成に調整した溶融金属を凝固させた後、さらにＥＳＲ法（エレクトロスラグ再溶解法）またはＶＡＲ法（真空アーク再溶解法）にて再精錬した後、従来の連続鋳造法に従いスラブを得た。表１に示すように、成分の異なる溶製材として溶製材１と溶製材２を準備した。 On the other hand, as a comparative material, continuously cast slab material conforming to the conventional manufacturing method is made by solidifying molten metal adjusted to the composition shown in Table 1, and then further using the ESR method (electro slag remelting method) or the VAR method (vacuum arc remelting method). After refining using the melting method), a slab was obtained according to the conventional continuous casting method. As shown in Table 1, ingot material 1 and ingot material 2 were prepared as ingot materials having different components.
　得られた試験材を圧延、焼鈍などの加工を施し合金箔にした。表２に各試験材の加工条件を示す。 The obtained test material was subjected to processing such as rolling and annealing to form an alloy foil. Table 2 shows the processing conditions for each test material.
　ＨＩＰ１およびＨＩＰ２の試験材を機械加工により厚さ１ｍｍ、３ｍｍ、１０ｍｍ、５０ｍｍの直方体形状に成形し合金板を得た。厚さ５０ｍｍの合金板は熱間圧延により厚さ３ｍｍの合金板にした。その他の厚さの合金板は熱間圧延をしなかった。こうして得られた厚さ１ｍｍ、３ｍｍ、および１０ｍｍの合金板を冷間圧延し、最終板厚３０μｍ（０．０３０ｍｍ）のＦｅ－Ｎｉ合金箔を得た。なお、冷間圧延の途中で中間焼鈍を行ったものと、中間焼鈍を行わなかったものを準備した。 The HIP1 and HIP2 test materials were machined into rectangular parallelepiped shapes with thicknesses of 1 mm, 3 mm, 10 mm, and 50 mm to obtain alloy plates. The 50 mm thick alloy plate was hot rolled into a 3 mm thick alloy plate. Alloy plates of other thicknesses were not hot rolled. The thus obtained alloy plates with thicknesses of 1 mm, 3 mm, and 10 mm were cold rolled to obtain Fe--Ni alloy foils with a final plate thickness of 30 μm (0.030 mm). In addition, two types were prepared: one in which intermediate annealing was performed during cold rolling, and the other in which intermediate annealing was not performed.
　一方、従来の製造方法に相当する溶製材については、連鋳後スラブ厚が２５０ｍｍであり、その後熱間圧延により板厚３００μｍ（０．３００ｍｍ）の合金板にし、（中間）冷間圧延、中間焼鈍、（最終）冷間圧延により最終板厚３０μｍ（０．０３０ｍｍ）のＦｅ－Ｎｉ合金箔を得た。 On the other hand, for the ingot material that corresponds to the conventional manufacturing method, the slab thickness after continuous casting is 250 mm, and then hot rolling is performed to form an alloy plate with a thickness of 300 μm (0.300 mm), (intermediate) cold rolling, intermediate An Fe-Ni alloy foil with a final thickness of 30 μm (0.030 mm) was obtained by annealing and (final) cold rolling.
　得られた各Ｆｅ－Ｎｉ合金箔の変形量を、前述したように鉛直方向吊り下げ試験により評価した。図２に、鉛直方向吊り下げ試験の概要を示す。合金箔を幅４０ｍｍ、長さ２５０ｍｍの短冊状に切断（長手方向が圧延方向になるように切断）したものを試験片１とし、これを鉛直定盤（鉛直方向に平行な平面（鉛直平面）を有する定盤）２の鉛直平面３に吊り下げた。鉛直平面３と試験片１との間の隙間５の隙間量を実測し、その最大値を以って変形量として評価した。本実施例では、１００ｇの重りを試験片下方端に付けて張力４を発生させ、図３に示すように試験片１と鉛直定盤２の鉛直平面３との間に生じた隙間５（図中の点線枠内）を隙間ゲージ（図示せず）により計測した。隙間５を計測する範囲６は特に限定しないが、鉛直平面３の全幅を測定範囲６とするとよく、本実施例もそのようにした。隙間ごとに４回計測しその平均を当該隙間の変形量とし、各隙間の変形量の最大値をその試験片の変形量として評価した。 The amount of deformation of each of the obtained Fe--Ni alloy foils was evaluated by a vertical hanging test as described above. Figure 2 shows an overview of the vertical hanging test. Test piece 1 was prepared by cutting alloy foil into strips with a width of 40 mm and a length of 250 mm (cut so that the longitudinal direction was in the rolling direction), and this was placed on a vertical surface plate (a plane parallel to the vertical direction (vertical plane)). It was suspended on a vertical plane 3 of a surface plate 2 having a surface plate. The amount of the gap 5 between the vertical plane 3 and the test piece 1 was actually measured, and the maximum value was evaluated as the amount of deformation. In this example, a 100 g weight was attached to the lower end of the test piece to generate tension 4, and a gap 5 was created between the test piece 1 and the vertical plane 3 of the vertical surface plate 2 as shown in FIG. (within the dotted line frame) was measured using a gap gauge (not shown). Although the range 6 in which the gap 5 is measured is not particularly limited, it is preferable to set the entire width of the vertical plane 3 as the measurement range 6, which is also the case in this embodiment. Each gap was measured four times and the average was taken as the amount of deformation of the gap, and the maximum value of the amount of deformation of each gap was evaluated as the amount of deformation of the test piece.
　平均陽電子消滅寿命（ＰＡＬ）は、前述したように、それぞれの試験材のＦｅ－Ｎｉ合金箔を１０ｍｍ角に切断し、これを３枚重ねたものを２組準備し、陽電子線源を３枚重ねのＦｅ－Ｎｉ合金箔で挟み、これをアルミ箔で包み固定しＰＡＬ測定用試料を作成した。準備した測定用試料を測定装置にかけて陽電子消滅寿命（ＰＡＬ）を測定した。ＰＡＬ測定装置としてテクノエーピー社製の陽電子消滅寿命装置を使用し、陽電子線源に２２Ｎａを用いて評価した。データ解析ソフトはデンマーク工科大学が開発したＰＡＬＳｆｉｔ３を用いた。測定に際してはカプトン膜寿命（０．３８００ｐｓ）やエポキシ寿命（１．９０４４ｐｓ）などの影響を考慮するため、これらの寿命を固定して材料については1成分で平均陽電子消滅寿命を解析した。 The average positron annihilation life (PAL) is calculated by cutting the Fe-Ni alloy foil of each test material into 10 mm squares, preparing two sets of three stacked sheets, and placing three sheets of positron beam source. A sample for PAL measurement was prepared by sandwiching between two layers of Fe--Ni alloy foil, and wrapping and fixing this with aluminum foil. The prepared measurement sample was applied to a measuring device to measure the positron annihilation lifetime (PAL). The evaluation was carried out using a positron annihilation lifetime device manufactured by Techno AP as a PAL measuring device and using 22 Na as a positron beam source. The data analysis software used was PALSfit3 developed by the Technical University of Denmark. In order to take into account the effects of Kapton membrane life (0.3800 ps) and epoxy life (1.9044 ps) during the measurement, these lives were fixed and the average positron annihilation life of the material was analyzed for one component.
　表２に各試験材の製造条件と変形量、ＰＡＬ（平均陽電子消滅寿命）の測定結果を示す。表２に示す変形量とＰＡＬの関係を図１に図示した。図１中の三角マークが比較例（溶製材）であり、丸マークが実施例（ＨＩＰ材）を示す。 Table 2 shows the manufacturing conditions, amount of deformation, and measurement results of PAL (average positron annihilation life) of each test material. The relationship between the amount of deformation shown in Table 2 and PAL is illustrated in FIG. The triangular mark in FIG. 1 indicates a comparative example (molten material), and the circular mark indicates an example (HIP material).
　表２および図１から分かるように、平均陽電子消滅寿命（ＰＡＬ）と変形量には相関があり、ＰＡＬが長寿命化すると変形量が小さくなることが分かる。従来品相当の比較例１と比較すると分かるようにＨＩＰ処理した実施例はどれもＰＡＬが０．１５０ｎｓｅｃ以上であり、変形量の比較例１に比べ小さくなっていることが確認できた。また、成分組成の観点からほぼ同等の合金元素が添加されているＨＩＰ１に係る実施例１～６と溶製材２の比較例３を対比しても、ＨＩＰ材の方が、ＰＡＬが長く変形量が小さいことが確認できた。 As can be seen from Table 2 and FIG. 1, there is a correlation between the average positron annihilation lifetime (PAL) and the amount of deformation, and it can be seen that the amount of deformation becomes smaller as the life of PAL becomes longer. As can be seen from the comparison with Comparative Example 1, which corresponds to the conventional product, all of the HIP-treated examples had a PAL of 0.150 nsec or more, and it was confirmed that the amount of deformation was smaller than that of Comparative Example 1. In addition, even when comparing Examples 1 to 6 of HIP1, in which almost the same alloying elements are added from the viewpoint of composition, and Comparative Example 3 of ingot material 2, HIP material has a longer PAL and deformation amount. was confirmed to be small.
　本発明は、Ｆｅ－Ｎｉ合金箔に利用することができる。特に板厚が５０μｍ以下の極薄Ｆｅ－Ｎｉ合金箔に利用するとその効果が顕著になる。 The present invention can be utilized for Fe-Ni alloy foil. The effect is particularly noticeable when used for ultra-thin Fe--Ni alloy foils with a thickness of 50 μm or less.
１　　 試験片
２　　 鉛直定盤
３　　 鉛直平面
４　　 張力（の方向）
５　　 隙間
６　　 測定範囲 1 Test piece 2 Vertical surface plate 3 Vertical plane 4 Tension (direction)
5 Gap 6 Measuring range

Claims (9)

  1. 　成分が、質量％で、
    Ｃ　：０～０．０３０％、
    Ｓｉ：０～０．２１％、
    Ｍｎ：０～０．３０％、
    Ｎｉ：３０．０～６０．０％、
    Ｃｏ：０～５．００％、
    Ｐ　：０．０１％以下、
    Ｓ　：０．０１％以下、および
    残部がＦｅおよび不純物であり、
    板厚が５０μｍ以下であって、陽電子消滅寿命が０．１５０ｎｓ以上であることを特徴とするＦｅ－Ｎｉ合金箔。     The ingredients are mass%,
    C: 0 to 0.030%,
    Si: 0 to 0.21%,
    Mn: 0 to 0.30%,
    Ni: 30.0 to 60.0%,
    Co: 0-5.00%,
    P: 0.01% or less,
    S: 0.01% or less, and the remainder is Fe and impurities,
    An Fe--Ni alloy foil having a thickness of 50 μm or less and a positron annihilation life of 0.150 ns or more.
  2. 　前記陽電子消滅寿命が０．１５０ｎｓ～０．２００ｎｓである請求項１に記載のＦｅ－Ｎｉ合金箔。 The Fe--Ni alloy foil according to claim 1, wherein the positron annihilation lifetime is 0.150 ns to 0.200 ns.
  3. 　前記板厚が２０μｍ以下の請求項１または２に記載のＦｅ－Ｎｉ合金箔。 The Fe-Ni alloy foil according to claim 1 or 2, wherein the plate thickness is 20 μm or less.
  4. 　請求項１または２に記載のＦｅ－Ｎｉ合金箔の製造方法であって、
    成分が、質量％で、
    Ｃ　：０～０．０３０％、
    Ｓｉ：０～０．２１％、
    Ｍｎ：０～０．３０％、
    Ｎｉ：３０．０～６０．０％、
    Ｃｏ：０～５．００％、
    Ｐ　：０．０１％以下、
    Ｓ　：０．０１％以下、および
    残部がＦｅおよび不純物であるＦｅ－Ｎｉ合金粉末を準備する工程と、
    前記Ｆｅ－Ｎｉ合金粉末をＨＩＰ法によりＦｅ－Ｎｉ合金塊を製造するＦｅ－Ｎｉ合金塊製造工程と、前記Ｆｅ－Ｎｉ合金塊を圧延する圧延工程を含むことを特徴とするＦｅ－Ｎｉ合金箔の製造方法。     A method for producing a Fe-Ni alloy foil according to claim 1 or 2, comprising:
    The ingredients are mass%,
    C: 0 to 0.030%,
    Si: 0 to 0.21%,
    Mn: 0 to 0.30%,
    Ni: 30.0 to 60.0%,
    Co: 0-5.00%,
    P: 0.01% or less,
    A step of preparing Fe-Ni alloy powder in which S: 0.01% or less and the balance is Fe and impurities;
    An Fe-Ni alloy foil comprising a step of manufacturing an Fe-Ni alloy ingot by using the Fe-Ni alloy powder by HIPing the Fe-Ni alloy powder, and a rolling step of rolling the Fe-Ni alloy ingot. manufacturing method.
  5. 　さらに、前記圧延工程の各圧延パス間または最終圧延後に少なくとも１回の焼鈍工程を含む請求項４に記載のＦｅ－Ｎｉ合金箔の製造方法。 The method for producing Fe--Ni alloy foil according to claim 4, further comprising at least one annealing step between each rolling pass of the rolling step or after the final rolling.
  6. 　前記板厚が２０μｍ以下の請求項４に記載のＦｅ－Ｎｉ合金箔の製造方法。 The method for producing an Fe-Ni alloy foil according to claim 4, wherein the plate thickness is 20 μm or less.
  7. 　前記板厚が２０μｍ以下の請求項５に記載のＦｅ－Ｎｉ合金箔の製造方法。 The method for manufacturing an Fe-Ni alloy foil according to claim 5, wherein the plate thickness is 20 μm or less.
  8. 　請求項１または２に記載のＦｅ－Ｎｉ合金箔を有する部品。 A component comprising the Fe-Ni alloy foil according to claim 1 or 2.
  9. 　前記Ｆｅ－Ｎｉ合金箔の板厚が２０μｍ以下である請求項８に記載の部品。 The component according to claim 8, wherein the Fe-Ni alloy foil has a thickness of 20 μm or less.
PCT/JP2023/021715 2022-06-30 2023-06-12 Iron–nickel alloy foil, method for manufacturing iron–nickel alloy foil, and component WO2024004613A1 (en)

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Publication number Priority date Publication date Assignee Title
JP2007231423A (en) * 1994-12-27 2007-09-13 Imphy Usine Precision Process for manufacturing shadow mask made of iron/nickel alloy
WO2020067537A1 (en) * 2018-09-27 2020-04-02 日鉄ケミカル＆マテリアル株式会社 Metal mask material, method for producing same, and metal mask
JP2022512583A (en) * 2018-11-19 2022-02-07 エルジー イノテック カンパニー リミテッド Alloy metal plate and mask for vapor deposition containing it
WO2022244701A1 (en) * 2021-05-17 2022-11-24 日鉄ケミカル＆マテリアル株式会社 Ferrous alloy foil, manufacturing method therefor, and component using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007231423A (en) * 1994-12-27 2007-09-13 Imphy Usine Precision Process for manufacturing shadow mask made of iron/nickel alloy
WO2020067537A1 (en) * 2018-09-27 2020-04-02 日鉄ケミカル＆マテリアル株式会社 Metal mask material, method for producing same, and metal mask
JP2022512583A (en) * 2018-11-19 2022-02-07 エルジー イノテック カンパニー リミテッド Alloy metal plate and mask for vapor deposition containing it
WO2022244701A1 (en) * 2021-05-17 2022-11-24 日鉄ケミカル＆マテリアル株式会社 Ferrous alloy foil, manufacturing method therefor, and component using same

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